Halogenized vat dyestuffs and process of making same.



UNETED fiTATEbtPdEENT tlFFit/E.

GADIEN'I ENGI AND JAROSLAV FRGHLICH, OF BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN BASLE, F BASEL SWITZERLAND.

HALOGENIZED VAT DYESTUFFS AND PROCESS or ivranxnoisamn.

No Drawing.

To all whom it may concern:

Be it known that We, Games r Emu, doctor 0t'-philosophy and chemist, a citizen of the Swiss :Republic; and Janosmv From L on, docto.r,fot' philosophy and cheniistg a subject of. the Emperor of I Auslrial-ltuugary, residents of Basel. Switzerland. have invented new and useful Halogenized Vat Dyestufis and a Process of Making Same. of which the following is a full clear, and exact specification.

In the specification of our application for R Letters Patent filed December 28th 1910,

'densation in that they furnish, generally nets possessing the valuable yielding ontreatment with reducing agents,

we have described the manufacture of new colored condensation products by treating an indigo substance with a halid of an acid of the aromatic series, in the presence of a condensing agent, the said condensing prodproperty of leuco compounds soluble in alkalis anddye ing Vegetable and animal fibers in an allialine vat beautiful. yellow tints of excellent fastness. According to'the present invention these condensation products can be transformedby treatment with halogensor substances yielding halogens, into new halogenized derivatives, also constituting valuable dyestuffs dyeing in a vat but distin-- guished from the parent products of conspeaking. purer and in part much redder tints, and possess a greater aflinity, particularly for vegetable fibers.

The invention is illustrated by the following examples, the partsbcing by weight:

l lxample I 10 parts/oil the dvesliuti 'ob t-ained inac Ordance with Example "I oi the aloresaid specification by action of benzoyl chlorul on indigo, are mixed with parts of nitrobenzene and 1520 parts of bromin and the mixture is'first stirred for about 1: hours at the ordinary temperature; it is then heated on the oil bath for 3-5 hours at ITO-175 C. When the mass has been cooled the brominated product which has separated is filtered, wa bed with alcohol or steamed for the purp-se of eliminating adherent nitrobenzene,an dried.

The new dyestut'f is a 'ellow crystalline powder containing about per cent. of bromin. In concentrated ulfuric acid it dissolves to .a brown-red .sc ution; when the tated' as yellow flocks.

solution is diluted-the d'yi stuff :is precipi- Si furic' acid eon-- ingr.

crease of .weurht Specification of Letters i atent. PatQilf-Qdj Ji ly 11, 1'91 1 Application filed April 24, 1911. Serial 623;0l1i6:' 1 i taining 24 per cent." of siilfuric anhydriddissolves the dycstufl' to ail intense bluish red solutum; \Vilh alkaline reducing agents the dyestu it jiehls a 'wine-red vatwhich dyes vegetable'and animal fibers pure yellow tints .ofexcellent fastress and much more reddish tluurthose obtained with the dyestuii used as parent material.

Example ll: Into a mixture of l25'parts of concentrated sulfuric acid and 10 parts of bromin, there are introduced 5 parts of the dyestufl obtained according to Example I of the aforesaid specification, care being taken to stir well stii.'ring is continued for 1::"20 hours at the ordinary temperature (15--20 (3.). The niassis then poured into water, the whole filtered and the solid inat- .ter washed until the washings are neutral. The dycstutl' paste ried or usedzas-such for dyeing or print- The brominatcd dyestuif, thus prepared, dissolves in turning sulfuric acid to a-b1'own-redsolution and yiel'ds on textile.

fibers yellow tints a little less greenish than those obtainedwith the bromo derivative made accordinl to Example I.

Example Ill: 20 parts of the product obtained according"to'EXample I of the aforesaid specification are introduced little by little into 150200 parts of bromin; care being taken to stir well and to cool the mass slightly. The mixture is first stirred for 10 to 12 hours at the ordinary temperature, then heated inthe course of 2-3 hours to gentle boiling in. a reflux apparatus and 'ruaiutained for 10-15 hours at the'boiline' point of. bromin; I The .,.cc..s oi bromiu is then separated by distillation, the residue is treated with a dilute solution ot' sodium bisulfitc, the liquid filtered" and the solid washed with 'hot water. The'brominated dyestufl thus obtained has properties analogous to those of tho brominated product made in accordance with Example I.

Example iv: 20 parts of the condensation product from indigo and benzoyl chlorid. made in accordance with the aforesaid specification. iitrobenzene duccd during;

and into the mixture is introabout. 15 minutes a moderately .strong current o't'ohloriu. care being taken to stir and to cool \Vltll ice; the current of chlorin is continued until there an inamounting to about 12 parts; The chlorin is then stopped and the are suspended in 100 parts oi J mixture is stirred first for 12 to 15 hours while cooling externally and then for -15 v whereupon it constitutes a clear yellow crystalline powder containing some 14-16 per cent. of chlorin; itdyes cotton and wool in an alkaline vat yellow ti' ts more reddish than those obtained with the dyestutf used as the parent material.

If in the preceding example a larger proportion of bromjn or chlorin is used, or if the operation is conducted at a higher temperature, if necessary under pressure and with aid of a carrier of halogen, more highly brominated or chlorinated products are obtained.

Instead of the diluents used in the examples, other suitable solvents or diluents may be used, such as for exam 1e glacial acetic acid, carbon bisulfid, car on tetrachlorid, pentachlorethane, dichlorobenzene, sulfuryl chlorid, chlorosulfonic acid, or fuming sulfuric acid. When using sulfuric acid, chlorosulfonic acid or fuming sulfuric acid, hydro- -bromic acid may be used as the brominating agent and may be produced wlthln the mass by introducing a metal bromid such as sodium bromid, for instance.

In an analogous manner other condensation products from indigo and its derivatives obtainable in accordance with the aforesaid specification may be transformed into halogenized derivatives. Mixed halogenized products may also be made by the process of the present invention by subjecting feebly chlorinated or brominated products to a subsequent bromination or chlorination. The chloro-bromo derivatives thus obtained have properties analogous to those of tliederivatives which are brominated or chlorinated in corresponding degree. e

What we claim is:

1. The described process for the manufacture of new halogenated yellow vat-dyestuffs which' process consists in acting with a halogenating agent on the condensation products obtainable by treating an indigo substance with a halid of an acid of the aromatic series in the presence of a condensing agent.

2. The described process for the manufacture of new halogenized yellow vat-dyestufis, consisting in acting with a halogenating agent on the condensation roducts obtamed by treating indigo -w1th benzoylchlorid in the presence of acondensing agent.

3. As new products the described halogenated yellow vat-dyestufis, derived from the hereinbefore defined condensation prodacts of indigo substances and aromatic acid halids, forming in dry state yellow powders, insoluble in water, dilficult-ly soluble in alcohol, more easily soluble in hot nitrobenzene with a yellow color, dissolving in concen tratcd sulfuric acid with brownish-red color, in fuming sulfuric acid with bluish-red color and yielding by treatment with alkaline reducing agents wine-red to Bordeaux-red solutions, from which vegetable and animal fibers are first dyed in Bordeaux-red to winered shades, becoming yellow on exposure to the air, the said yellow shades being fast to washing, light and chlorin. v

4. As new articles of manufacture, the described halogenated vat-dyestuffs derivedfrom the hereinbefore defined condensation product of indigo and benzoyl chlorid, form ing in dry state yellow powders, insoluble in water, diflicultly soluble in alcohol, more easily soluble in hot nitrobenzene with a yellow color, dissolving in concentrated sulfuric acid with brownish-red color, in fuming sulfuric acid with bluish-red color and yield- -ing by treatment with alkaline reducing agents wine-red to Bordeaux-red solutions, from which vegetable and animal fibers; are first dyed in Bordeaux-red to wine-red shades, becoming yellow on exposure to the air, the said yellow shades ibeing fast to washing, light and chlorin. I v

In witness whereof we have signed our names this 7th day of April 1911, in the-v presence of two subscribing witnesses.

GADIENT ENGI. JAROSLAV rRoHLIon.

Witnesses:

(-lnonun (harem), An AND R rr'rnn. 

